JP2002212415A - Urethane resin-based curable resin composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane resin-based curable resin composition excellent in adhesion to a wide range of materials such as metals, plastics, woods, inorganic materials and the like. SOLUTION: The composition comprises as its ingredients a urethane resin, comprising as the main chain a polyoxyalkylene polymer containing at least a polyoxyethylene and bearing an -RN-CO-NH- bond (R is a specific substituent) and a hydrolyzable silicon group in its molecule, and a vinyl polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane resin-based curable resin composition, and more particularly, to an excellent adhesiveness to a wide range of materials such as metals, plastics, woods, and inorganic materials, and particularly to adhesives and sealing materials. And a urethane resin-based curable resin composition suitable for paints and the like.

[0002]

2. Description of the Related Art A polyoxyalkylene polymer having a hydrolyzable silicon group at a terminal, which is also called a modified silicone resin, is a liquid polymer, and its cured product retains flexibility even at a relatively low temperature. Therefore, it is widely used for sealing materials, adhesives, coating agents and the like. However, the polyoxyalkylene polymer having a hydrolyzable silicon group has a problem that adhesion to plastic is inferior.
It has also been attempted to improve the adhesive strength by blending a polymer obtained by polymerizing a polymerizable unsaturated group-containing monomer with the polyoxyalkylene polymer having a hydrolyzable silicon group. However, adhesion to plastic is still insufficient.

[0003] On the other hand, silylated urethane resins having a polyoxyalkylene structure in the main chain and having a silicon-reactive group, which are obtained by reacting an isocyanate group-terminated urethane prepolymer with aminosilane or mercaptosilane, are also known. . Although this silylated urethane resin has a urethane bond and thus has excellent adhesion to plastics, it cannot be said that adhesion to metals is satisfactory.

[0004]

An object of the present invention is to provide a urethane resin-based curable resin composition having excellent adhesion to a wide range of materials such as metals, plastics, wood, and inorganic materials.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and as a result, have found that the main chain is a polyoxyalkylene polymer containing at least polyoxyethylene, A resin composition containing, as components, a urethane resin having a -RN-CO-NH- bond (R is a specific substituent) and a hydrolyzable silicon group, and a vinyl polymer can achieve the object of the present invention. The present invention has been found.

That is, the present invention relates to (a) a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene, and represented by the following general formulas (1) and (2) in the molecule. Urethane-based resin (A)
And

Embedded image

Embedded image However, R ¹ represents the following general formula (3), the following general formula (4), the following general formula (5) or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and R ² represents a 1 to 20 carbon atoms. X represents a substituted or unsubstituted organic group, X represents a hydroxyl group or a hydrolyzable group,
n represents 0, 1 or 2, respectively.

Embedded image

Embedded image

Embedded image Here, R ³ is a hydrogen atom or —COOR ¹⁰ , R ⁴ is a hydrogen atom or a methyl group, R ⁵ is —COOR ¹¹ or a nitrile group, and R ⁶ is a substituted or unsubstituted 2-C 1-20 carbon atom. R ⁷ represents an organic group which may contain a silicon atom having a molecular weight of 500 or less, R ⁸ and R ⁹ represent the above general formula (3) or the following general formula (6), and R ¹⁰ and R ¹¹ represents an organic group having a molecular weight of 500 or less.

Embedded image (B) The gist of the present invention is a urethane resin-based curable resin composition containing, as a component, a vinyl polymer (B) obtained by polymerizing a polymerizable vinyl group-containing monomer (compound (a)).

Further, the present invention provides a method for producing the urethane resin-based curable resin composition comprising polymerizing the compound (a) in the urethane resin (A) (hereinafter referred to as Production Method 1). ).

Further, the present invention relates to a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene, wherein a group selected from a hydroxyl group, a mercapto group and a primary amino group or a secondary amino group in the molecule. The compound (a) is polymerized in a compound having at least one compound (compound (b)), and then reacted with a polyisocyanate compound (compound (c)) to produce a urethane prepolymer (C). The method for producing the urethane resin-based curable resin composition (hereinafter referred to as Production Method 2), comprising reacting the polymer (C) with a compound (Compound (d)) represented by the following general formula (7). Make a summary.

Embedded image However, R ¹ , R ² and n have the same meaning as defined in claim 1, Y is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, the following general formula (8) or the following general formula: Equation (9) is
Shown respectively.

Embedded image

Embedded image However, R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as defined in claim 1, and R ¹² and R ¹³ represent a substituted or unsubstituted divalent organic group having 1 to 10 carbon atoms. .

Further, the present invention provides a method for reacting the above compound (b) with the above compound (c) to obtain a urethane prepolymer (C).
, The compound (a) is polymerized in the urethane prepolymer (C), and the compound (d) is further reacted with the method for producing the urethane resin-based curable resin composition (hereinafter referred to as production). This is referred to as Law 3.)

[0010] The present invention further comprises the step of polymerizing the compound (a) in the compound (b) and then reacting the compound (compound (e)) represented by the following general formula (10). The gist of the present invention is a method for producing a urethane resin-based curable resin composition (hereinafter referred to as Production Method 4).

Embedded image However, R ¹ , R ² , X and n have the same meanings as in claim 1 and Y has the same meaning as in claim 3, respectively, and Z represents a residue other than an isocyanate group of the compound (c). , M is 1, 2 or 3.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane resin-based curable resin composition of the present invention is (a) a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene. And a urethane-based resin (A) having a group represented by the general formula (2) and (b) a vinyl polymer (B) obtained by polymerizing the compound (a) as components.

R ¹ , R ² , X and n in the above general formulas (1) and (2) representing the urethane resin (A) are as described above, and the hydrolyzable group of X is
Examples thereof include an alkoxy group, an acetoxy group, and an oxime group, and an alkoxy group is particularly preferable. The urethane resin (A) is a known resin. Typically, (1) the compound (b) is reacted with the compound (c) to produce a urethane prepolymer (C), and then the compound (d) is prepared. And (2) reacting the compound (b) with the compound (e).

The vinyl polymer (B) is a polymer of the compound (a), which is a polymerizable vinyl group-containing monomer. Examples of the compound (a) include acrylic acid, methacrylic acid, acrylic ester or methacrylic ester ( Hereinafter, these are referred to as (meth) acrylates), styrene-based compounds, acrylonitrile, α-methylacrylonitrile,
2,4-dicyanobutene-1, vinylpyrrolidone, vinylcarbazole, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, acrylamide, Methacrylamide, vinyl glycidyl ether,
Allyl glycidyl ether, methacryl glycidyl ether, vinyl chloride, vinyl acetate, vinyl propionate,
Butadiene, isoprene, chloroprene; other olefins, unsaturated esters, halogenated olefins, vinyl ethers and the like.

As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, Hexadecyl (meth) acrylate, octadecyl (meth) acrylate, etc., alkyl esters of acrylic acid or methacrylic acid having 1 to 20 carbon atoms in the alkyl group; cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate,
Phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate,
Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl acrylate, tert-butylaminoethyl methacrylate, cyclohexylaminoethyl acrylate, cyclohexylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, allyl acrylate, allyl Methacrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxy-3
-Phenoxypropyl acrylate, 2-hydroxy-
3-phenoxypropyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trade name: M-110, manufactured by Toagosei Co., Ltd.
And M-111, trade names, manufactured by Shell Chemical Co., Ltd .: VEOBA 9 and VEOBA 10, trifluoroethyl methacrylate and the like.

Examples of the styrene compound include styrene, vinyltoluene, divinylbenzene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene and the like. . Among them, acrylonitrile, styrene, glycidyl methacrylate, carbon
Preferred are alkyl esters of up to 20 acrylic or methacrylic acids. These polymerizable vinyl group-containing monomers (compound (a)) are not limited to one kind, and two or more kinds can be used.

As the compound (a), a vinyl group-containing monomer having a hydrolyzable silicon group can also be used. Examples of the vinyl group-containing monomer include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, tris (2-methoxyethoxy) vinylsilane, 3-acryloyloxypropylmethyldimethoxysilane, and 3-methacryloyloxypropylmethyldimethoxysilane. , 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and the like. Among them, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyl Trimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane are particularly preferred.

As the polymerization method for the polymerizable vinyl group-containing monomer (a), any of the known methods such as radical polymerization, anionic polymerization, and cationic polymerization, which are generally used for the polymerization of these monomers, can be employed. In particular, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-
Dimethylvaleronitrile), 2,2'-azobis (2-
Methyl-4-trimethoxysilylpentonitrile),
2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), trade name of Wako Pure Chemical Industries, Ltd .:
VA-046B, VA-057, VA-061, VA-
085, VA-086, VA-096, V-601, V
A radical polymerization method, which is performed in the presence of a peroxide polymerization initiator such as azo compounds such as -65 and VAm-110, benzoyl peroxide, t-alkylperoxyester, acetyl peroxide, and diisopropyl peroxycarbonate, is preferable. . At this time, lauryl mercaptan, γ
-Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, thio-β-naphthol, thiophenol, n-butylmercaptan, ethylthioglycolate, isopropylmercaptan, t
The polymerization can be carried out in the presence of a chain transfer agent such as -butyl mercaptan or γ-trimethoxysilylpropyl disulfide. The polymerization reaction is carried out at 20 to 200 ° C., particularly
It is preferable to carry out at a temperature of 150 ° C. for several hours to several tens hours. Further, the polymerization can be carried out in the presence of a solvent such as xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate and the like. These solvents, after the end of the polymerization,
If necessary, the curable resin composition of the present invention may be removed by a method such as distillation under reduced pressure, or may be mixed with the urethane resin (A) without removing these solvents.

The urethane resin-based curable resin composition of the present invention is obtained by blending a urethane resin (A) and a vinyl polymer (B), and the blending ratio of both is 100%. 5 parts by weight of vinyl polymer (B)
To 500 parts by mass, preferably 10 to 200 parts by mass. If the blending amount of the vinyl polymer (B) is less than 5 parts by mass,
Adhesion to metal becomes insufficient, and when it exceeds 500 parts by mass, internal curability becomes insufficient. The urethane resin-based curable resin composition of the present invention is prepared by blending the urethane resin (A) and the vinyl polymer (B), and is prepared by the above-mentioned production method (1), the above-mentioned production method (2), It can be prepared by the production method (3) or the production method (4).

The production method (1) comprises polymerizing the compound (a) in the urethane resin (A), and the polymerization method of the compound (a) in the urethane resin (A) is as follows. The method may be the same as the method of polymerizing the compound (a) to obtain a vinyl polymer (B).

The compound (b) used in the production method (2) is a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene, and has a hydroxyl group, a mercapto group, a primary amino group or It is a compound having one or more groups selected from secondary amino groups.

The polyoxyalkylene polymer used as a raw material of the compound (b) is preferably a hydroxyl-terminated polymer produced by reacting a monoepoxide with an initiator in the presence of a catalyst. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used. As the monoepoxide, ethylene oxide is used as an essential component, and propylene oxide, butylene oxide, hexylene oxide and the like, tetrahydrofuran and the like can be used in combination. Examples of the catalyst include alkali metal catalysts such as potassium compounds and cesium compounds, complex metal cyanide complex catalysts, and metal porphyrin catalysts.

The raw material polyoxyalkylene polymer has a number average molecular weight of 500 to 30,000, especially
It is preferred to use those of 000 to 20,000.
In order to make a relatively low molecular weight product produced using an alkali metal catalyst into a high molecular weight product, it is possible to increase the amount by reacting a polyhalogen compound such as methylene chloride. The polyoxyalkylene polymer produced using the double metal cyanide complex catalyst is generally of a high molecular weight. As the double metal cyanide complex catalyst, a complex containing zinc hexacyanocobaltate as a main component, and an ether and / or alcohol complex are preferable. The composition of the ether and / or alcohol complex is essentially the same as in JP-B-46-2.
What is described in 7250 gazette can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during production of the complex. As the alcohol, for example, those described in JP-A-4-145123 can be used, and tert-butanol is particularly preferable.

The starting polyoxyalkylene polymer preferably has two or more functional groups. Specifically, polyoxyethylene or at least 1% by mass of polyoxyethylene is used.
Including polyoxypropylene, polyoxybutylene,
Copolymers such as polyoxyhexylene and polyoxytetramethylene are exemplified. Preferred raw material polyoxyalkylene polymers are di- to hexa-valent polyoxypropylene polyols, particularly polyoxypropylene diol and polyoxypropylene triol, and a total of 100 parts by mass of oxypropylene and oxyethylene in the polyoxypropylene polyol. Oxyethylene is 1 part by mass or more, preferably 3 to 80 parts by mass. Compound (b) is commercially available, and these can be used in the present invention. The method of polymerizing the compound (a) in the compound (b) in the production method (2) may be the same as the method of polymerizing the compound (a) to obtain a vinyl polymer (B).

In the above production method (2), after the above compound (a) is polymerized in the above compound (b), it is reacted with a polyisocyanate compound (compound (c)) to produce a urethane prepolymer (C). And urethane prepolymer (C)
And a compound represented by the above general formula (7) (compound (d))
To react. Examples of the compound (c) used for producing the urethane prepolymer (C) include a diisocyanate compound, a polysocyanate compound excluding the diisocyanate compound, and the like. As the diisocyanate compound, for example, aliphatic,
Alicyclic, araliphatic, aromatic diisocyanate compounds and the like can be mentioned. Hereinafter, specific examples thereof will be described.

Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate and the like. Alicyclic diisocyanate compound: 1,3-cyclopentene diisocyanate, 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-
3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like. Aromatic diisocyanate compound: 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,
ω'-diisocyanate-1,4-diethylbenzene,
1,3- or 1,4-bis (1-isocyanate-
1-methylethyl) benzene or a mixture thereof. Aromatic diisocyanate compound: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 '
-Diphenyl diisocyanate, 1,5-naphthalenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4,
4'-diphenyl ether diisocyanate and the like.

Examples of the polyisocyanate compound excluding the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds. Hereinafter, specific examples thereof will be described.

Aliphatic polyisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,3 6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane and the like. Alicyclic polyisocyanate compound: 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethyl isocyanate cyclohexane, 3-isocyanate-
3,3,5-trimethylcyclohexyl isocyanate, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2, 6
-Di (isocyanatomethyl) -bicyclo [2,2
1] heptane, 5- (2-isocyanatoethyl) -2
-Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2
-Isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl ) -Bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane and the like. Aromatic polyisocyanate compound: 1,
3,5-triisocyanatomethylbenzene and the like. Aromatic polyisocyanate compound: triphenylmethane-4,
4 ', 4 "-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4'-diphenylmethane-2,2',
5,5'-tetraisocyanate and the like. Other polyisocyanate compounds: diisocyanates containing a sulfur atom such as phenyldiisothiocyanate.

The compound (b) is reacted with the compound (c) in the presence of the vinyl polymer (B) obtained by polymerizing the compound (a) to form a urethane prepolymer (C).
May be produced according to the usual method for producing a urethane prepolymer by reacting a polyol compound and a polyisocyanate compound.

The compound (d) to be reacted with the urethane prepolymer (C) is represented by the above general formula (7). In the general formula (7), R ¹ represents the above general formula (3), (4) represented by the above formula (5) or a substituted or unsubstituted organic group having 1 to 20 carbon atoms. Specific examples of the compound (d) represented by the general formula (7) include N-
Phenyl-γ-aminopropyltrimethoxysilane, N
-Phenyl-γ-aminopropylmethyldimethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane, N- (n-butyl) -3-aminopropylmethyldimethoxysilane, and the like. It can be manufactured by a method.

(1) R ¹ is represented by the above general formula (3),
Compound in which Y is a divalent organic group Primary amino group and silicon group containing a hydrolyzable group or silicon group containing a hydroxyl group (preferably silicon group containing a hydrolyzable group)
(Compound (f)), and one or more selected from α, β-unsaturated carbonyl compound (compound (g)), maleic diester (compound (h)) and acrylonitrile in a chemical equivalent thereof. (2) A compound in which R ¹ is represented by the above general formula (3) and Y is the above general formula (8): primary amino group, secondary amino group and hydrolysis (Compound (i)) each having one silicon group containing a functional group or a silicon group containing a hydroxyl group (preferably a silicon group containing a hydrolyzable group), and a primary amino group and a secondary compound in the compound (i). A method in which an amino group is reacted with one or more compounds selected from chemical equivalents of compound (g), compound (h) and acrylonitrile (3) R ¹ is represented by the above general formula (3), and Y is Formula represented by general formula (9) Object compound (i), the compound (i) primary amino group and a chemical equivalent of the compound in (g), after reaction of the compound (h) and one or more selected from acrylonitrile,
A compound represented by the formula R ^{7 in a} chemical equivalent to the secondary amino group in the compound (i)
Method for reacting a monoisocyanate compound (compound (j)) represented by NCO (R ⁷ is as defined above) (4) R ¹ is represented by the above general formula (4), and Y is a divalent organic group A method of reacting compound (i) with a primary amino group in compound (i) and a chemical equivalent of compound (j) (5) wherein R ¹ is represented by the above general formula (5), and R ⁸ and R ⁹ in the general formula (5) are represented by the general formula (3);
A compound in which Y is a divalent organic group, a compound (i), a primary amino group in the compound (i) and 2
A method of reacting one or two or more compounds selected from a chemical equivalent of compound (g), compound (h) and acrylonitrile (6) R ¹ is represented by the above general formula (5), and the general formula (5) Wherein R ⁸ is represented by the general formula (3), R ⁹ is represented by the general formula (6), and Y is a divalent organic group. The compound (i) and the compound (i) After reacting a primary amino group with one or more chemical equivalents of compound (g), compound (h) and acrylonitrile,
Method of reacting a secondary amino group generated by this reaction with a chemical equivalent of compound (j)

Examples of the compound (f) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane and the like.

Examples of the compound (g) include (meth) acrylic compounds, vinyl ketone compounds, vinyl aldehyde compounds, and other compounds. As (meth) acrylic compounds, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth)
Acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) ) Acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, Carboxymethyl ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadienyl
(Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylate, isoacetone Butoxymethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformaldehyde, N, N-dimethylacrylamide, t-octylacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7 -Amino-3,7-dimethyloctyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, acryloylmo Other such Hollin, Toagosei Chemical Industry Co., Ltd. under the trade name: Aronix M-102, M-1
11, M-114, M-117, manufactured by Nippon Kayaku Co., Ltd .: Kayahard TC110S, R629, R644,
Trade name: VISCOAT 3700 manufactured by Osaka Organic Chemical Company, etc.

Further, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylate to glycidyl ether of bisphenol A ) Polyfunctional compounds such as acrylates and commercial products of the polyfunctional compounds, trade names of Mitsubishi Chemical Corporation: Iupima UV, SA1002, SA2
007, trade name: Viscort 70, manufactured by Osaka Organic Chemical Company
0, Nippon Kayaku product name: Kayahard R604, D
PCA-20, DPCA-30, DPCA-60, DP
CA-120, HX-620, D-310, D-33
0, trade name of Toagosei Chemical Industry Co., Ltd .: Aronix M-
210, M-215, M-315, M-325 and the like.

In addition to the above compounds, γ-methacryloxypropyltrimethoxysilane having an alkoxysilyl group, γ-methacryloxypropyltriethoxysilane,
γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane, and the like.

Examples of the vinyl ketone compound include vinyl acetone, vinyl ethyl ketone, vinyl butyl ketone and the like.
Examples of vinylaldehyde compounds include acrolein, methacrolein, and crotonaldehyde, and examples of other compounds include maleic anhydride, itaconic anhydride, itaconic acid, crotonic acid, N-methylolacrylamide, diacetoneacrylamide, and N- [3- (Dimethylamino) propyl] methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-
t-octylacrylamide, N-isopropylacrylamide and the like.

In addition to the above compounds, compounds containing a fluorine atom, a sulfur atom or a phosphorus atom therein are also included. Examples of the compound containing a fluorine atom include perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and examples of the compound containing a phosphorus atom include (meth) acryloxyethyl phenyl acid phosphate.

Among the above compounds (g), methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, t-butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like are preferred. Of these, methyl acrylate and ethyl acrylate are particularly preferred for imparting rapid curability, and 2-ethylhexyl acrylate and lauryl acrylate are particularly preferred for imparting flexibility. Compound (g) can be used alone or in combination of two or more.

Compound (h) (maleic acid diester) includes dimethyl maleate, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate,
Dioctyl maleate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, ease of reaction,
Dimethyl maleate, diethyl maleate, dibutyl maleate, and di-2-ethylhexyl maleate are preferred from the viewpoint of wide commercial availability. Compound (h) can be used alone or in combination of two or more.

Compound (i) includes N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ
-Aminopropylmethyldiethoxysilane, and other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM
6063, X-12-896, KBM576, X-12
-565, X-12-580, X-12-5263, K
BM6123, X-12-575, X-12-562,
X-12-5202, X-12-5204, KBE97
03 and the like.

Of the above compounds (i), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ,
N-β (aminoethyl) -γ-aminopropyltriethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane are preferred.

Compound (j) includes ethyl isocyanate, n-hexyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-hexyl isocyanate, benzyl isocyanate, 2-methoxyphenyl isocyanate and the like. In addition, isocyanate silanes such as Shin-Etsu Chemical's trade name: KBM9007 (γ-isocyanatopropyltrimethoxysilane).

The reaction between the urethane prepolymer (C) and the compound (d) is performed at 50 to 100 ° C. for 30 minutes to 3 hours.

The above-mentioned production method (3) comprises the above-mentioned compound (b)
And the above compound (c) to produce a urethane prepolymer (C), and then polymerize the above compound (a) in the urethane prepolymer (C) to produce a vinyl polymer (B). Reacting with compound (d).
The reaction between the compound (b) and the compound (c) is carried out by reacting the compound (b) in which the vinyl polymer (B) is present in the above-mentioned production method (2) with the compound (c). The method for producing the vinyl polymer (B) by polymerizing the compound (a) may be the same as the above method, and the method for further reacting the compound (d) with the compound (d) is as described above. It may be the same as the case of the reaction between the urethane prepolymer (C) and the compound (d) in the production method (2).

The above-mentioned production method (4) comprises the above-mentioned compound (b)
After the above compound (a) is polymerized therein to produce a vinyl polymer (B), it is reacted with a compound (e) represented by the above general formula (10). The compound (e) represented by the general formula (10) can be produced by reacting the compound (d) with the compound (c).
The compound (d) and the compound (c) are reacted with the compound (d) by 1 mol per 1 mol of the compound (c). Here, m represents m defined by the general formula (10). The reaction between the compound (d) and the compound (c) is performed at 30 to 90 ° C. for 30 minutes to 3 hours.
Done for hours.

The curable resin composition of the present invention contains the urethane resin (A) and the vinyl polymer (B) as active ingredients. In addition to these active ingredients, a curing catalyst and a filler may be used if necessary. Agents and various additives.

As the above-mentioned curing catalyst which can be optionally contained, an organotin compound, a metal complex, a basic compound, an organic phosphorus compound and water (moisture in the air) can be used. Specifically, as the organotin compound, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, dibutyltin oxide, dibutyltin oxide and Reaction products with phthalic acid diester are exemplified. As the metal complex, tetrabutyl titanate, tetraisopropyl titanate, titanate compounds such as triethanolamine titanate, lead octylate, lead naphthenate,
Carboxylic acid metal salts such as nickel naphthenate, cobalt naphthenate, bismuth octylate, and bismuth versatate; metal acetylacetonate complexes such as aluminum acetylacetonate complex and vanadium acetylacetonate complex; As the basic compound, γ-
Aminosilanes such as aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; DABCO (registered trademark) series manufactured by Sankyo Air Products; DABCO B
L-series, linear or cyclic tertiary amines containing plural nitrogens, such as 1,8-diazabicyclo [5.4.0] undec-7-ene, and quaternary ammonium salts. As the organic phosphorus compound, monomethyl phosphoric acid, di-n-
Butylphosphoric acid, triphenyl phosphate and the like. The compounding ratio of the curing catalyst is 100 parts of the active ingredient of the curable resin composition.
It is 0.01 to 10 parts by mass per part by mass.

Examples of the filler include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica, various balloons and the like.

The various additives include a plasticizer, an additive, a solvent, a dehydrating agent and the like. Examples of the plasticizer include phthalic esters such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic esters such as dioctyl adipate and dibutyl sebacate. As the above additives, antioxidants, thixotropic agents, ultraviolet absorbers, pigments, various tackifiers,
Examples include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins such as bisphenol A type and bisphenol F type. Aminosilane is particularly preferred as the silane coupling agent. Any solvent may be used as long as it has good compatibility with the curable resin composition and the like and has a water content of 500 ppm or less. Examples of the dehydrating agent include quick lime, orthosilicate, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkylalkoxysilanes, various vinylalkoxysilanes, and the like.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. (Example 1) (Synthesis of urethane resin) (1) Polyoxypropylene diol having a number average molecular weight of 4,000 (Takelac P-28, trade name: manufactured by Takeda Pharmaceutical Co., Ltd., oxypropylene (hereinafter referred to as PO) / Oxyethylene (hereinafter referred to as EO) (mass ratio) = 100 /
0) was converted to 2,000 g of a polyoxypropylene triol having a number average molecular weight of 3,400 (ADEKA polyether GR-
3308, trade name: Asahi Denka Kogyo KK, PO / EO = 2 /
8), 1,700 g, Sumijur T-80 (trade name:
348.4 g of Sumitomo Bayer Urethane Co., Ltd.) was reacted at 90 ° C. for 3 hours with stirring in a nitrogen atmosphere to obtain a urethane prepolymer (1). (2) KBM902 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., γ-
Aminopropylmethyldimethoxysilane) to 163.3
g and 2-ethylhexyl acrylate at a rate of 184.3 g at 23 ° C. for 7 days to obtain a reaction product (1-1). (3) The urethane prepolymer (1) was reacted at a rate of 1,000 g and the reactant (1-1) at a rate of 171.2 g at 90 ° C. for 1 hour with stirring in a nitrogen atmosphere to obtain an isocyanate group (NCO). Was obtained as a liquid urethane-based resin (1).

(Synthesis of vinyl polymer) (4) 485 g of n-butyl acrylate, 10 g of lauryl mercaptan, and 5 g of azobisisobutyronitrile
The mixed solution was prepared at a rate of 100 g, and 200 g of the mixed solution was put into a reaction vessel, reacted at 100 ° C. for 1 hour, and then 300 g of the mixed solution was added dropwise over 2 hours. The reaction was carried out for an hour to obtain a vinyl polymer (1). (Preparation of Composition) After mixing 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1), 500 g of calcium carbonate (NS400, trade name: made by Shiraishi Industry Co., Ltd.) and treated calcium carbonate (white luster CCR, trade name) : Shiraishi Industry Co., Ltd.) 500 g in a planetary mixer
After dehydration by heating at 00 ° C., the mixture was cooled to room temperature and KBM903
(Trade name: Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane) 50 g, KBM403 (trade name: Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane) 30 g and Stan No. 918 (product name:
10 g of an organic tin catalyst (manufactured by Sankyoki Gosei Co., Ltd.) was kneaded to obtain a urethane resin composition.

Example 2 (1) A reaction vessel was charged with an aromatic hydrocarbon solvent (Hisol 29).
2, 100 g of brand name (manufactured by Nippon Petrochemical Co.)
After heating to 00 ° C, n-butyl acrylate 485
g, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile were added dropwise over 3 hours, and further reacted at 100 ° C. for 2 hours to produce a viscous liquid. The solvent was distilled off with an aspirator to obtain a vinyl polymer (2). (2) Instead of vinyl polymer (1), vinyl polymer (2)
A urethane-based resin composition was obtained in the same manner as in Example 1 except for using.

Example 3 (1) 500 g of a urethane-based resin (1) was placed in a nitrogen atmosphere for 1 hour.
The mixture was heated to 00 ° C., and a mixed solution of 485 g of n-butyl acrylate, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile was added dropwise over 5 hours.
The mixture was reacted at 2 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (2) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Example 4 (1) 211 g of polyoxypropylene diol used in Example 1 and 179 g of polyoxypropylene triol used in Example 1 were charged into a reaction vessel and heated to 100 ° C., and then n- 485 g of butyl acrylate, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile
Is added dropwise over 5 hours, and the mixture is further reacted at 100 ° C. for 2 hours to obtain a reactant (4-1) containing a vinyl polymer.
I got (2) 890 g of the reaction product (4-1) and Sumidur T
-80 was mixed at a rate of 36.7 g and reacted at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere to obtain a urethane prepolymer (4) containing a vinyl polymer. (3) 926.7 g of the urethane prepolymer (4) and 73.3 g of the reaction product (1-1) obtained in Example 1 were mixed and reacted at 90 ° C. for 1 hour while stirring under a nitrogen atmosphere. Thus, a liquid urethane resin (4) in which all NCO was silylated was obtained. (4) In the same manner as in Example 1 except that 1,000 g of the urethane-based resin (4) obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1). Thus, a urethane resin composition was obtained.

Example 5 (1) 211 g of a polyamine compound having a number average molecular weight of 4,000 (Jeffamine D-4000, trade name, manufactured by Sankyo Texaco Chemical Co., Ltd.), and 6.6 of n-butyl acrylate.
The reaction was carried out at a rate of 76 g to obtain a reaction product (5-1). 217.76 g of the reaction product (5-1) and 179 g of the polyoxypropylene triol used in Example 1 were charged into a reaction vessel and heated to 100 ° C., and then 485 g of n-butyl acrylate, 10 g of lauryl mercaptan, and azobisisopropyl A mixed solution of 5 g of butyronitrile was added dropwise over 5 hours, and the mixture was further reacted at 100 ° C. for 2 hours to obtain a reaction product (5-2) containing a vinyl polymer. (2) 896.76 g of the reaction product (5-2) and 36.7 g of Sumidur T-80 were mixed, and reacted at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere to contain a vinyl polymer. A urethane prepolymer (5) was obtained. (3) 933.46 g of the urethane prepolymer (5) and 73.3 g of the reaction product (1-1) obtained in Example 1 were mixed and reacted at 90 ° C. for 1 hour while stirring under a nitrogen atmosphere. Thus, a liquid urethane resin (5) in which all NCO was silylated was obtained. (4) In the same manner as in Example 1 except that 1,000 g of the urethane-based resin (5) obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1). Thus, a urethane resin composition was obtained.

Example 6 (1) 211 of a polythiol compound having a number average molecular weight of 4,000 (LP-55, trade name: manufactured by Toray Thiokol Co., Ltd.)
g and 179 g of the polyoxypropylene triol used in Example 1 were charged into a reaction vessel and heated to 100 ° C., and a mixed solution of 485 g of n-butyl acrylate, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile was added for 5 hours. Then, the mixture was further reacted at 100 ° C. for 2 hours to obtain a reaction product (6-1) containing a vinyl polymer. (2) 890 g of the reaction product (6-1) and Sumidur T
-80 was mixed at a rate of 36.7 g, and reacted at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere to obtain a urethane prepolymer (6) containing a vinyl polymer. (3) 926.7 g of the urethane prepolymer (6) and 73.3 g of the reaction product (1-1) obtained in Example 1 were mixed and reacted at 90 ° C. for 1 hour while stirring under a nitrogen atmosphere. Thus, a liquid urethane resin (6) in which all NCOs were silylated was obtained. (4) In the same manner as in Example 1 except that 1,000 g of the urethane-based resin (6) obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1). Thus, a urethane resin composition was obtained.

Example 7 (1) The urethane prepolymer (1) obtained in Example 1 was replaced with 4
26.7 g was charged into a reaction vessel, and 100 ° C. under a nitrogen atmosphere.
Then, a mixed solution of 485 g of n-butyl acrylate, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile was added dropwise over 5 hours, and further heated at 100 ° C.
For 2 hours, and reacting the vinyl polymer-containing reactant (7
-1) was obtained. (2) A mixture of 926.7 g of the reaction product (7-1) and 73.3 g of the reaction product (1-1) obtained in Example 1 was reacted at 90 ° C. for 1 hour while stirring under a nitrogen atmosphere. Let N
A liquid urethane resin (7) in which all of the CO was silylated was obtained. (3) In the same manner as in Example 1 except that 1,000 g of the urethane-based resin (7) obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1). Thus, a urethane resin composition was obtained.

Example 8 (1) 73.3 g of the reaction product (1-1) obtained in Example 1 and 36.7 g of Sumidur T-80 were mixed,
The reaction was carried out at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere.
Reaction product (8-1) was obtained. (2) A mixture of 890 g of the reaction product (4-1) obtained in Example 4 and 110 g of the reaction product (8-1) obtained above was mixed,
The reaction was carried out at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere.
A liquid urethane resin (8) was obtained. (3) In the same manner as in Example 1 except that 1,000 g of the urethane-based resin (8) obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1). Thus, a urethane resin composition was obtained.

Example 9 (1) 163.3 g of KBM902 and 100.1 g of ethyl acrylate were reacted at 23 ° C. for 7 days to obtain a reaction product (9-1). (2) The urethane prepolymer (1) was reacted at a rate of 1,000 g and the reactant (9-1) at a rate of 130.2 g at 90 ° C. for 1 hour with stirring in a nitrogen atmosphere, and all NCO was silyl. A liquid urethane-based resin (9) was obtained. (3) 500 g of urethane resin (9) in a nitrogen atmosphere 1
Heated to 00 ° C., 242.5 g of methyl methacrylate,
A mixed solution of 242.5 g of 2-ethylhexyl acrylate, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile was added dropwise over 5 hours, and further reacted at 100 ° C. for 2 hours to mix a urethane resin containing a vinyl polymer. A solution was obtained. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Example 10 (1) A reaction product (10-1) was obtained by reacting KBM902 at a rate of 163.3 g and dimethyl maleate at a rate of 144.1 g at 23 ° C. for 7 days. (2) The urethane prepolymer (1) was reacted at a rate of 1,000 g and the reactant (10-1) at a rate of 151.8 g at 90 ° C. for 1 hour with stirring in a nitrogen atmosphere to remove all NCO silyl. A liquid urethane-based resin (10) was obtained. (3) 500 g of a urethane-based resin (10) was heated to 100 ° C. in a nitrogen atmosphere, and 200 g of n-butyl acrylate was added.
200 g of lauryl acrylate, 85 g of KBM503 (trade name: γ-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), 10 g of lauryl mercaptan
And a mixed solution of 5 g of azobisisobutyronitrile was added dropwise over 5 hours, and further reacted at 100 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

(Example 11) (1) KBM602 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., N-
β (aminoethyl) -γ-aminopropylmethyldimethoxysilane) was reacted at a rate of 206.4 g and 2-ethylhexyl acrylate at a rate of 368.6 g at 23 ° C. for 7 days to obtain a reaction product (11-1). . (2) 1,000 g of the urethane prepolymer (1), the reactant (11-
1) was reacted at 90 ° C. for 1 hour with stirring in a nitrogen atmosphere at a rate of 284 g to obtain a liquid urethane resin (11) in which all NCO was silylated. (3) 500 g of the urethane-based resin (11) was heated to 100 ° C. in a nitrogen atmosphere, and methyl methacrylate
g, 242.5 g of lauryl acrylate, KBM803
A mixed solution of 10 g (trade name: Shin-Etsu Chemical Co., Ltd., γ-mercaptopropyltrimethoxysilane) and 5 g of azobisisobutyronitrile was added dropwise over 5 hours.
The mixture was reacted at 0 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Example 12 (1) A reaction product (12-1) was obtained by reacting KBM602 at 206.4 g and ethyl acrylate at 200.2 g at 23 ° C. for 7 days. (2) The urethane prepolymer (1) was reacted at a rate of 1,000 g and the reactant (12-1) at a rate of 200.8 g at 90 ° C. for 1 hour with stirring in a nitrogen atmosphere to obtain all NCO silyl. Thus, a liquid urethane resin (12) was obtained. (3) 500 g of the urethane-based resin (12) was heated to 100 ° C. in a nitrogen atmosphere, and n-butyl acrylate 242.5
g, cyclohexyl methacrylate 242.5 g, lauryl mercaptan 10 g, and 2,2'-azobis (2-
Methyl-4-trimethoxysilylpentonitrile) 5 g
Was added dropwise over 5 hours, and the mixture was further reacted at 100 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Example 13 (1) 206.4 g of KBM602 and 288.2 g of dimethyl maleate were reacted at 23 ° C. for 7 days to obtain a reaction product (13-1). (2) The urethane prepolymer (1) was reacted at a rate of 1,000 g and the reactant (13-1) at a rate of 244.4 g at 90 ° C. for 1 hour with stirring in a nitrogen atmosphere to remove all NCO silyl. A liquid urethane-based resin (13) was obtained. (3) 500 g of the urethane-based resin (13) was heated to 100 ° C. in a nitrogen atmosphere to obtain 2-ethylhexyl acrylate 2
42.5 g, tetrahydrofuran methacrylate 24
A mixed solution of 2.5 g, 10 g of γ-trimethoxysilylpropyl disulfide (DSPTMS) and 5 g of azobisisobutyronitrile was added dropwise over 5 hours.
The mixture was reacted at 2 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Example 14 (1) 1,000 g of urethane prepolymer (1)
126. BM573 (trade name: N-phenyl-γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
1 g at 90 ° C. with stirring under a nitrogen atmosphere.
The reaction was carried out for an hour to obtain a liquid urethane resin (14) in which all NCOs were silylated. (2) 500 g of the urethane-based resin (14) was heated to 100 ° C. under a nitrogen atmosphere to obtain isobornyl methacrylate 24.
A mixed solution of 2.5 g, 242.5 g of lauryl acrylate, 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile was added dropwise over 5 hours, and the mixture was further reacted at 100 ° C. for 2 hours to obtain a urethane resin containing a vinyl polymer. Was obtained. (3) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Example 15 (1) The reaction product (1-1) obtained in Example 1 was used for 347.
6 g, Sumidur T-80 in a ratio of 174.2 g,
The mixture was reacted at 90 ° C. for 3 hours with stirring under a nitrogen atmosphere to obtain a reaction product (15-1). (2) 2,000 g of polyoxypropylene diol used in Example 1, 1,700 g of polyoxypropylene triol used in Example 1, and reactant (15-1) 1,0
43.6 g, 90% with stirring under a nitrogen atmosphere.
Reaction for 3 hours at ℃, liquid urethane resin (15)
I got (3) 500 g of the urethane-based resin (15) was heated to 100 ° C. under a nitrogen atmosphere, and 485 g of n-butyl acrylate was added.
A mixed solution of 10 g of lauryl mercaptan and 5 g of azobisisobutyronitrile was added dropwise over 5 hours.
The mixture was reacted at 0 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

(Example 16) (1) The reaction product (13-1) obtained in Example 13 was converted to 49
A reaction product (16-1) was obtained by reacting 4.6 g of Sumidur T-80 in a ratio of 174.2 g at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere. (2) 2,000 g of polyoxypropylene diol used in Example 1, 1,700 g of polyoxypropylene triol used in Example 1, and reactant (16-1) 1,3
37.7 g at 90% with stirring under a nitrogen atmosphere.
Reaction for 3 hours at ℃, liquid urethane resin (16)
I got (3) 500 g of the urethane-based resin (16) was heated to 100 ° C. in a nitrogen atmosphere to obtain 2-ethylhexyl acrylate 2
42.5 g, tetrahydrofuran methacrylate 24
A mixed solution of 2.5 g, 10 g of DSPTMS and 5 g of azobisisobutyronitrile was added dropwise over 5 hours.
The mixture was reacted at 00 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (4) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Comparative Example 1 (1) 4,000 g of polyoxypropylene diol and 348.4 g of Sumidur T-80 used in Example 1
At 90 ° C. while stirring under a nitrogen atmosphere.
The reaction was carried out for an hour to obtain a urethane prepolymer (A). (2) 1,000 g of the urethane prepolymer (A) and 171.2 g of the reaction product (1-1) obtained in Example 1 were mixed and reacted at 90 ° C. for 3 hours while stirring under a nitrogen atmosphere. Thus, a urethane-based resin (A) in which all NCO was silylated was obtained. (3) In the same manner as in Example 1 except that 1,000 g of the urethane-based resin (A) obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1). Thus, a urethane resin composition was obtained.

Comparative Example 2 (1) Comparative Example 1 500 g of the obtained urethane resin (A) was heated to 100 ° C. in a nitrogen atmosphere, and 485 g of n-butyl acrylate, 10 g of lauryl mercaptan and azobisisobutyronitrile were obtained. 5 g of the mixed solution was added dropwise over 5 hours, and the mixture was further reacted at 100 ° C. for 2 hours to obtain a mixed solution of a urethane resin containing a vinyl polymer. (2) In the same manner as in Example 1 except that 1,000 g of the mixed solution obtained above was used instead of the mixture of 500 g of the urethane-based resin (1) and 500 g of the vinyl polymer (1),
A urethane resin composition was obtained.

Comparative Example 3 Urethane Resin (1) 500
g and vinyl polymer (1) instead of a mixture of 500 g,
A urethane-based resin composition was obtained in the same manner as in Example 1, except that 1,000 g of the urethane-based resin (1) obtained in Example 1 was used.

Comparative Example 4 Urethane Resin (1) 500
g and vinyl polymer (1) instead of a mixture of 500 g,
Oxyalkylene polymer having a hydrolyzable silicon group (M
A-903, trade name: manufactured by Kanegafuchi Chemical Co., Ltd.) 1,000 g
A urethane-based resin composition was obtained in the same manner as in Example 1 except for using.

Using the urethane resin compositions obtained in the above Examples and Comparative Examples, an Asada / stainless steel plate, an Asada / ABS resin plate or an Asada / acryl resin plate was adhered as an adherend. After curing for 7 days at 60 ° C. and a relative humidity of 60%, the tensile shear bond strength (N / cm ² ) was measured according to JIS K 6850. The results are shown in Tables 1 and 2. In addition, an Asada / steel plate or Asada / SBR rubber plate was bonded as the adherend,
After curing for 7 days at a relative humidity of 60%, the peel adhesion strength (N / 25 mm) was measured according to JIS K 6854. The results are shown in Tables 3 and 4.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

As is clear from Tables 1 to 4, the composition comprising a urethane polymer having a polyoxyethylene skeleton and a vinyl polymer exhibits a well-balanced adhesion performance to various adherends. You can see that.

[0076]

The urethane resin-based curable resin composition of the present invention has excellent adhesion to a wide range of materials such as metals, plastics, wood, and inorganic materials, and is particularly suitable for applications such as adhesives, sealing agents, and paints. Are suitable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Shinichi Sato 5-3-35 Nishibori, Urawa-shi, Saitama F-term (reference) in Company Urawa Research Laboratories 4J002 AC03X AC06X AC09X BC02X BC08X BC09X BD05X BE04X BF01X BF02X BG01X BG03X BG04X BG05X BG06X BG07X BG10X BG13X BH02X BJ00X CK04 BA02AC01 BA49 BB01 EA09 EA10 GA06 4J034 BA03 DB04 DB05 DB07 DC50 DG03 DG04 DG05 DG06 DG08 DG10 HA01 HA02 HA07 HA09 HA11 HA15 HC01 HC03 HC12 HC22 HC52 HC61 HC64 HC65 HC71 MA22 QA07 RA07 RA08

Claims (5)

[Claims] 1. A polyurethane having a polyoxyalkylene polymer whose main chain contains at least polyoxyethylene, and having in its molecule a group represented by the following general formula (1) or (2): Resin (A) and Embedded image However, R ¹ represents the following general formula (3), the following general formula (4), the following general formula (5) or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and R ² represents a 1 to 20 carbon atoms. X represents a substituted or unsubstituted organic group, X represents a hydroxyl group or a hydrolyzable group,
n a is 0, 1 or 2, respectively, when R ² there are a plurality may be different and those R ² the same, X their X may be the same or different when there are multiple. Embedded image Embedded image Embedded image Here, R ³ is a hydrogen atom or —COOR ¹⁰ , R ⁴ is a hydrogen atom or a methyl group, R ⁵ is —COOR ¹¹ or a nitrile group, and R ⁶ is a substituted or unsubstituted 2-C 1-20 carbon atom. the valent organic group, R ⁷ is also a good organic group optionally containing a molecular weight of 500 or less silicon atoms, R ⁸ and R ⁹ are the above-mentioned general formula (3) or the following general formula (6), respectively, R ⁸ and R ⁹ may be the same or different. R ¹⁰ and R ¹¹ each represent an organic group having a molecular weight of 500 or less. Embedded image (B) A urethane resin-based curable resin composition containing, as a component, a vinyl polymer (B) obtained by polymerizing a polymerizable vinyl group-containing monomer (compound (a)). 2. The method for producing a urethane resin-based curable resin composition according to claim 1, comprising polymerizing the compound (a) in the urethane resin (A). 3. A polyoxyalkylene polymer having a main chain containing at least polyoxyethylene, and having at least one group selected from a hydroxyl group, a mercapto group and a primary amino group or a secondary amino group in the molecule. After polymerizing the above compound (a) in a compound having the compound (compound (b)), it is reacted with a polyisocyanate compound (compound (c)) to produce a urethane prepolymer (C), and further, a urethane prepolymer (C) The method for producing a urethane resin-based curable resin composition according to claim 1, comprising reacting a compound (compound (d)) represented by the following general formula (7) with: Embedded image However, R ¹ , R ² and n have the same meaning as defined in claim 1, Y is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, the following general formula (8) or the following general formula: Equation (9) is
Shown respectively. Embedded image Embedded image However, R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as defined in claim 1, and R ¹² and R ¹³ represent a substituted or unsubstituted divalent organic group having 1 to 10 carbon atoms. . 4. After reacting the compound (b) with the compound (c) to obtain a urethane prepolymer (C), the compound (a) is polymerized in the urethane prepolymer (C). The method for producing a urethane resin-based curable resin composition according to claim 1, comprising reacting the compound (d). 5. The compound (a) in the compound (b)
The method for producing a urethane resin-based curable resin composition according to claim 1, comprising reacting a compound (compound (e)) represented by the following general formula (10) after polymerizing the compound. Embedded image However, R ¹ , R ² , X and n have the same meanings as in claim 1 and Y has the same meaning as in claim 3, respectively, and Z represents a residue other than an isocyanate group of the compound (c). , M is 1, 2 or 3.